I. Brihuega

Atomic-scale control of graphene magnetism by using hydrogen atoms.

Hydrogen atom makes graphene magnetic Graphene has many extraordinary mechanical and electronic properties, but its not magnetic. To make it so, the simplest strategy is to modify its electronic structure to create unpaired electrons. Researchers can do that by, for example, removing individual carbon atoms or adsorbing hydrogen onto graphene. This has to be done in a very controlled way because of a peculiarity of the graphenes crystal lattice, which consists of two sublattices. Gonzales-Herrero et al. deposited a single hydrogen atom on top of graphene and used scanning tunneling microscopy to detect magnetism on the sublattice lacking the deposited atom (see the Perspective by Hollen and Gupta). Science, this issue p. 437; see also p. 415 Scanning tunneling microscopy shows that a hydrogen atom deposited on graphene makes the complementary sublattice magnetic. [Also see Perspective by Hollen and Gupta] Isolated hydrogen atoms absorbed on graphene are predicted to induce magnetic moments. Here we demonstrate that the adsorption of a single hydrogen atom on graphene induces a magnetic moment characterized by a ~20–millielectron volt spin-split state at the Fermi energy. Our scanning tunneling microscopy (STM) experiments, complemented by first-principles calculations, show that such a spin-polarized state is essentially localized on the carbon sublattice opposite to the one where the hydrogen atom is chemisorbed. This atomically modulated spin texture, which extends several nanometers away from the hydrogen atom, drives the direct coupling between the magnetic moments at unusually long distances. By using the STM tip to manipulate hydrogen atoms with atomic precision, it is possible to tailor the magnetism of selected graphene regions.

Point defects on graphene on metals.

Understanding the coupling of graphene with its local environment is critical to be able to integrate it in tomorrows electronic devices. Here we show how the presence of a metallic substrate affects the properties of an atomically tailored graphene layer. We have deliberately introduced single carbon vacancies on a graphene monolayer grown on a Pt(111) surface and investigated its impact in the electronic, structural, and magnetic properties of the graphene layer. Our low temperature scanning tunneling microscopy studies, complemented by density functional theory, show the existence of a broad electronic resonance above the Fermi energy associated with the vacancies. Vacancy sites become reactive leading to an increase of the coupling between the graphene layer and the metal substrate at these points; this gives rise to a rapid decay of the localized state and the quenching of the magnetic moment associated with carbon vacancies in freestanding graphene layers.

Electronic and structural characterization of divacancies in irradiated graphene

This work was supported by Spain’s MICINN under Grants No. MAT2010-14902, No. CSD2010-00024, and No. CSD2007-00050, and by Comunidad de Madrid under Grant No. S2009/MAT-1467. M.M.U., I.B., F.H, P.M, J.Y.V., and J.M.G.R. also acknowledge the PHC Picasso program for financial support (project No. 22885NH).M.M.U. acknowledges financial support from MEC under FPU Grant No. AP-2004-1896. I.B. was supported by a Ramon y Cajal project of the Spanish MEC. F.H. held a doctoral support from the Region Rhone-Alpes

Observation of shell effects in superconducting nanoparticles of Sn

In a zero-dimensional superconductor, quantum size effects (QSE) not only set the limit to superconductivity, but are also at the heart of new phenomena such as shell effects, which have been predicted to result in large enhancements of the superconducting energy gap. Here, we experimentally demonstrate these QSE through measurements on single, isolated Pb and Sn nanoparticles. In both systems superconductivity is ultimately quenched at sizes governed by the dominance of the quantum fluctuations of the order parameter. However, before the destruction of superconductivity, in Sn nanoparticles we observe giant oscillations in the superconducting energy gap with particle size leading to enhancements as large as 60%. These oscillations are the first experimental proof of coherent shell effects in nanoscale superconductors. Contrarily, we observe no such oscillations in the gap for Pb nanoparticles, which is ascribed to the suppression of shell effects for shorter coherence lengths. Our study paves the way to exploit QSE in boosting superconductivity in low-dimensional systems.

Quasiparticle Chirality in Epitaxial Graphene Probed at the Nanometer Scale

Graphene exhibits unconventional two-dimensional electronic properties resulting from the symmetry of its quasiparticles, which leads to the concepts of pseudospin and electronic chirality. Here, we report that scanning tunneling microscopy can be used to probe these unique symmetry properties at the nanometer scale. They are reflected in the quantum interference pattern resulting from elastic scattering off impurities, and they can be directly read from its fast Fourier transform. Our data, complemented by theoretical calculations, demonstrate that the pseudospin and the electronic chirality in epitaxial graphene on SiC(0001) correspond to the ones predicted for ideal graphene.

Ethylene Irradiation: A New Route to Grow Graphene on Low Reactivity Metals

A novel technique for growing graphene on relatively inert metals, consisting in the thermal decomposition of low energy ethylene ions irradiated on hot metal surfaces in ultrahigh vacuum, is reported. By this route, we have grown graphene monolayers on Cu(111) and, for the first time, on Au(111) surfaces. For both noble metal substrates, but particularly for Au(111), our scanning tunneling microscopy and spectroscopy measurements provide sound evidence of a very weak graphene-metal interaction.

Tip and Surface Determination from Experiments and Simulations of Scanning Tunneling Microscopy and Spectroscopy

We present a very efficient and accurate method to simulate scanning tunneling microscopy images and spectra from first-principles density functional calculations. The wave functions of the tip and sample are calculated separately on the same footing and propagated far from the surface using the vacuum Green function. This allows us to express the Bardeen matrix elements in terms of convolutions and to obtain the tunneling current at all tip positions and bias voltages in a single calculation. The efficiency of the method opens the door to real time determination of both tip and surface composition and structure, by comparing experiments to simulated images for a variety of precomputed tips. Comparison with the experimental topography and spectra of the Si111-(7 x 7) surface shows a much better agreement with Si than with W tips, implying that the metallic tip is terminated by silicon.

Image potential states as a quantum probe of graphene interfaces

Image potential states (IPSs) are electronic states localized in front of a surface in a potential well, formed by the surface projected bulk band gap on one side and the image potential barrier on the other. In the limit of a two-dimensional solid, a double Rydberg series of IPSs has been predicted, which is in contrast to a single series present in three-dimensional solids. Here, we confirm this prediction experimentally for mono- and bilayer graphene. The IPSs of epitaxial graphene on SiC are measured by scanning tunneling spectroscopy and the results are compared with ab-initio band structure calculations. Despite the presence of the substrate, both calculations and experimental measurements show that the first pair of the double series of IPSs survives and eventually evolves into a single series for graphite. Thus, IPSs provide an elegant quantum probe of the interfacial coupling in graphene systems.

Role of pseudospin in quasiparticle interferences in epitaxial graphene probed by high-resolution scanning tunneling microscopy

Pseudospin, an additional degree of freedom emerging in graphene as a direct consequence of its honeycomb atomic structure, is responsible for many of the exceptional electronic properties found in this material. This paper is devoted to providing a clear understanding of how graphenes pseudospin impacts the quasiparticle interferences of monolayer (ML) and bilayer (BL) graphene measured by low-temperature scanning tunneling microscopy and spectroscopy. We have used this technique to map, with very high energy and space resolution, the spatial modulations of the local density of states of ML and BL graphene epitaxially grown on SiC(0001), in presence of native disorder. We perform a Fourier transform analysis of such modulations including wave vectors up to unit vectors of the reciprocal lattice. Our data demonstrate that the quasiparticle interferences associated to some particular scattering processes are suppressed in ML graphene, but not in BL graphene. Most importantly, interferences with 2(qF) wave vector associated to intravalley backscattering are not measured in ML graphene, even on the images with highest resolution where the graphene honeycomb pattern is clearly resolved. In order to clarify the role of the pseudospin on the quasiparticle interferences, we use a simple model which nicely captures the main features observed in our data. The model unambiguously shows that graphenes pseudospin is responsible for such suppression of quasiparticle interference features in ML graphene, in particular for those with 2qF wave vector. It also confirms scanning tunneling microscopy as a unique technique to probe the pseudospin in graphene samples in real space with nanometer precision. Finally, we show that such observations are robust with energy and obtain with great accuracy the dispersion of the p bands for both ML and BL graphene in the vicinity of the Fermi level, extracting their main tight-binding parameters.

Graphene Tunable Transparency to Tunneling Electrons: A Direct Tool To Measure the Local Coupling

The local interaction between graphene and a host substrate strongly determines the actual properties of the graphene layer. Here we show that scanning tunneling microscopy (STM) can selectively help to visualize either the graphene layer or the substrate underneath, or even both at the same time, providing a comprehensive picture of this coupling with atomic precision and high energy resolution. We demonstrate this for graphene on Cu(111). Our spectroscopic data show that, in the vicinity of the Fermi level, graphene π bands are well preserved presenting a small n-doping induced by Cu(111) surface state electrons. Such results are corroborated by Angle-Resolved Photoemission Spectra (ARPES) and Density Functional Theory with van der Waals (DFT + vdW) calculations. Graphene tunable transparency also allows the investigation of the interaction between the substrate and foreign species (such as atomic H or C vacancies) on the graphene layer. Our calculations explain graphene tunable transparency in terms of the rather different decay lengths of the graphene Dirac π states and the metal surface state, suggesting that it should apply to a good number of graphene/substrate systems.